AU660565B2 - Composition and procedure for the preparation of organic glasses - Google Patents

Abstract

A polymerizable liquid composition includes a polymerizable poly(allyl carbonate) of an aliphatic or cyclo-aliphatic polyol; an organic peroxide generator of free radicals selected from the group of perketals, and possibly an organic dye and/or an organic photochromic compound. The compositions can be transformed, by bulk polymerization, into an organic glass which is colourless, or coloured or photochromic, having good optical and mechanical characteristics. <IMAGE>

Description

AUSTRALIA

Patents Act 660565 COMPLETE SPECIFICATION

(ORIGINAL)

Class Int. Class Application Number: Lodged: Complete Specification Lodged: Accepted: Published: Priority Related Art: fe a 0 6.

.0 :00.: 0. 0.

a a. a Name of Applicant: Enichem Synthesis S.p.A.

Actual Inventor(s): Fiorenzo Renzi Claudio Gagliardi Franco Rivetti Pietro Allgrini Address for Service: PHILLIPS ORMONDE FITZPATRICK Patent and Trade Mark Attorneys 367 Collins Street Melbourne 3000 AUSTRALIA Invention 'itle: COMPOSITION AND PROCEDURE FOR THE PREPARATION OF ORGANIC

GLASSES

Our Ref 345922 POF Code: 1700/82363 The following statement is a full description of this invention, including the best method of performing it known to applicant(s): CASE 3590 COMPOSITION AND PROCEDURE FOR THE PREPARATION OF ORGANIC GLASS.

•The present invention relates to a liquid composition which can be polymerized via radicals into a 5 colourless, coloured or photochromic organic glass .e having good optical and mechanical characteristics. The invention also relates to a procedure for the preparation of said organic glass and the organic glass thus obtained.

10 Various organic polymers are used in the art such as organic glass for the optical field. Among these polyacrylates, polycarbonate and polystyrene can be cited. However the organic glass which is of greatest commercial interest is produced by the polymerization of allyl carbonates of diols or polyols, as disclosed for example by F. Stein in "Encyclopedia of Chemical Processing and Design", Ist Ed., Dekker Inc., N.Y., Vol. II, page 452 and the following; "Encyclopedia of Polymer Science and Technology" Vol. I, Interscience Publishers, New York, 1964, page 799 and the following; and also in European patent No. 35.304.

I~ II-- An allyl carbonate which is widely used for the purpose is bis(allyl carbonate) of diethylene glycol, owing to the optical and mechanical characteristics of the polymerized products which make it useful for the production of ophthalmic and safety plates and lenses.

However allyl carbonates of other aliphatic or cycloaliphatic diols and aliphatic polyols containing three or more hydroxyl groups in the molecule have also been used, with the aim of enhancing some of the characte- 10 ristics of organic glasses, such as abrasion resistance and thermal stability, or of reducing water absorption, as described for example in U.S. patents 4.713.433 and 4.874.821 and in European patent application No.

321.057.

15 An organic glass is generally prepared by bulk a polymerization of allyl carbonates, by the action of an initiator capable of generating free radicals under polymerization conditions, and it is known that the type of initiator used has a fundamental role. Conse- 0* 20 quently among the various groups of radicalic initiators currently available on the market, only a few are used industrially. Azo-derivatives, initiators of the peroxiketone type or hydroperoxides and peresters, such as ter-butyl perhexanoate, are totally ineffective or are not capable of bringing the degree of polymerization to sufficiently high levels, not even under conditions of high concentration.

I

Actually the industrial field almost exclusively uses initiators of the percarbonate type (for example di-isopropyl percarbonate, di-cyclo-hexyl percarbonate and di-sec.butyl percarbonate), which are soluble in allyl carbonates and ensure good characteristics of the polymeric products by a suitable choice of polymerizable allyl carbonates and polymerization conditions.

The use of percarbonates however has various disadvantages and involves the use of particularly severe 10 measures both in the storage and utilization steps. In *i particular storage temperatures are required which are lower than 0 C, or even lower than -15 C, as in the case of di-isopropyl percarbonate, the most widely used compound. The dissolution of percarbonates, which are crystalline solids, in allyl carbonates is a lengthy process, requiring several hours, especially in the case of allyl carbonates with a higher viscosity.

SConsequently to avoid the entry of air and humidity, which can impair the final characteristics of the 20 polymerized products, the dissolution is normally carried out in an inert environment, or under vacuum, with a consequent increase in costs. Finally to obtain an organic glass with good characteristics it is necessary to use a rather high concentration of initiators, normally about 3-5% by weight of the polymerizable composition.

As an alternative to percarbonates, in some cases the use of di-benzoyl peroxide Ls advised, which has a higher storage temperature than percarbonates. Dibenzoyl peroxide is normally sold as a mixture with a desensitizer (water or phthalates) which is capable of reducing the danger of and sensitivity to shock. The presence of a desensitizer however presents problems of incompatibility with the polymer of allyl carbonate, with the possibility of impairing its optical characteristics. In addition di-benzoyl peroxide, because of 10 its aromatic chemical nature, can affect the resistance to UV radiation of the polymer. In particular the polymerized products obtained with this kind of initiator, even if UV stabilizers are added, become evidently yellow after limited periods of exposure to UV rays.

S" 15 From what is described above, it is evidently necessary to improve the polymerizable compositions based on allyl carbonates and the procedures for the production of an organic glass, in order to overcome the disadvantages of the known art mentioned above.

20 The possibility of introducing photochromic compounds into an organic glass to give photochromic characteristics to the glass itself is also known in the art. There are numerous substances known which have photochromic characteristics, belonging to different classes of both inorganic and organic compounds, as mentioned in the texts "Photochromism" by G. H. Brown Vol. III of the series Weissberger "Techniques I Il of Organic Chemistry", Wiley Interscience, New York (1971) and in "Photochromism. Molecules and Systems", by H. Durr and H. Bouas-Laurent Vol. 40 of the series "Studies in Organic Chemistry", Elsevier (1990).

Among the photochromic compounds of an organic nature, those belonging to the classes of spiropyranes, spirooxazines, chromenes and fulgides are of industrial interest. Among these those belonging to the class of spiro-oxazines are particularly used, as these compounds combine a high photochromic activity and a .i better aging stability compared to other known organic a* 9* photochromic compounds, as described, for example, by H. Durr in Angew. Chem. Int. Ed. Engl., Vol. 28 (1989) pages 413-431, and by N.Y.C. Chu, in chapter 24 of the text "Photochromsim. Molecules and Systems", mentioned above.

The preparation of coloured organic glasses, using Sdyes which are mostly of an organic nature, is also known in the art.

20 In the case of organic glasses based on poly(allyl carbonates), the dye or photochromic compound is generally deposited in limited areas on the surface of or inside the preformed end-product (for example a lens) as described for example in U.S. patent 4.286.957 and in European patent application No. 141.407. There are various procedures used for the purpose which consist for example in an immersion of the organic L glass in a solution of the dye or photochromic substance in a suitable organic solvent. Techniques similzr to this are thermal transfer and transfer in a vapour phase of the dye or photochromic compound to the surface of the organic glass. Alternatively the dye or photochromic compound can be dispersed in paints or resins which are subsequently deposited in the form of a film on the organic glass. All these methods however are both laborious and costly. Moreover the dye or S" 10 photochromic compound is present in thin layers and generally on the surface of the end-product, thus affecting its stability. It is known, in fact, that atmospheric oxygen, mainly in its activated forms, greatly contributes to degrading the dye and photoo* 15 chromic compound. Contact with atmospheric oxygen can be avoided by preparing layered glass composed of two o* layers of organic glass between which the dye or •photochromic compound is inserted. It is evident however that this method is costly and laborious and 20 that the end-products obtained, being composed of different materials stvuck together with adhesives, tend to lose their structural unity or the positive characteristics of the organic glass.

A simple method for introducing a dye or photochromic compound into an organic glass consists in their insertion in bulk, by introducing them into the monomers subjected to polymerization. This technique produces acceptable results in preparing coloured or photochromic end-products from acrylic polymers, by casting (polymerization in a mould of mixtures of reactive monomer, polymerization initiator and dye or photochromic compound). When however a dye or photochromic compound is introduced into a polymerizable composition composed of an allyl carbonate of a polyol, such as bis(allyl carbonate) of diethylene glycol and a polymerization initiator, normally selected from diisopropyl percarbonate, dicyclohexyl percarbonate and dibenzoyl peroxide, and polymerization is then carried out by heating the resulting mixture, the articles obtained have a colouring or photochromic activity reduced to zero, probably owing to the degradation of 15 the dye or photochromic compound caused by the peroxide present.

It is therefore desirable to have compositions based on allyl carbonates and procedures for the production of organic glasses, which can contain the 20 dye or photochromic compound in bulk without the e disadvantages of the known art described above.

It has now been found, according to the present invention, that allyl carbonates of polyols polymerize under the action of reduced quantities of perketalic 25 polymerization initiators, producing organic glasses with good optical and mechanical characteristics.

Perketals are compounds which are normally liquid and I -rrs~L easily soluble in allyl carbonates. In addition they can be stored at relatively high temperatures (up to about 30 C).

It has also been found that this polymerization takes place without any substantial degradation of an organic dye or organic photochromic compound introduced into the polymerizable composition. It is therefore possible to incorporate the organic dye or photochromic compound in bulk and to obtain coloured or photochromic organic glasses in an easy and convenient way.

It has finally been found that this bulk incorporation enhances the colour or photochromic characteristics of organic glass and the duration of the photochromic activity, with respect to organic glasses of the known art containing the dye or photochromic e compound either on the surface or in limited areas of the glass.

In accordance with this, the first aspect of the present invention relates to a polymerizable liquid 20 composition which can be polymerized, via radicals, g into an organic glass, also coloured and/or photochromic, including a polymerizable allyl carbonate, a *g0 polymerization initiator capable of generating free radicals under polymerization conditions and possibly also a dye and/or photochromic compound, characterized *n in that: -e said polymerizable allyl carbonate is at least a poly(allyl carbonate) of an aliphatic C 3

-C

10 polyol, linear or branched, or of a cyclo-aliphatic

C

5

-C

16 polyol, said polyols containing from 2 to 6 hydroxyl groups in the molecule, said poly(allyl carbonates) being in the form of monomers or mixtures of monomer and relative oligomers; said polymerization initiator, generator of free radicals, is at least a compound selected from the group of perketals; said photochromic compound is at least an organic photochromic compound selected from the groups of spiropyranes, spiro-oxazines, chromenes and fulgides; and said dye is at least an organic dye.

Component (A) As stated above, the allyl carbonates which are suitable for the purposes of the present invention are poly(allyl carbonates) of aliphatic polyols containing from 3 to 10 carbon atoms in the linear or branched chain. Poly(allyl carbonates) of cyclo-aliphatic polyols containing from 5 to 16 carbon atoms in the molecule are also suitable for the purpose. These polyols may generally contain from 2 to 6 hydroxyl 25 groups in the molecule and preferably from 2 to 4. It is also possible to use mixed poly(allyl carbonates) i.e. deriving from two or more polyols, which can be I R I catained by the mechanical mixing of poly(allyl carbonates) of single polyols, or directly by chemical reaction starting from diallyl carbonate and a mixture of polyols, as is described in more detail later on.

Finally all these poly(allyl carbonates) can be in the form of a monomer, or a mixture of the monomer with the relative oligomers. In general poly(allyl carbonates) are liquid products at room temperature, with a viscosity of 10 to 500 cst, measured at 25*C and their oligomer content can vary within wide limits, for example from 0 to about 80% by weight.

In accordance with this, examples of poly(allyl carbonates) are: bis(allyl carbonates) of diols such as for example diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, 1,3-propandiol, 1,4butandiol, 1,5-pentandiol, 1,6-hexandiol, neopentyl glycol, 3-methyl-l,5-pentandiol, 2-methyl-2-ethyl-l,3propandiol, 2,2-diethyl-l,3-propandiol, 2,2,4-trimethyl-l,3-pentandiol, 1,4-diemthylolcyclohexane and 4,8bis(hydroxymethyl) 0 2 6 tricyclodecane; tris(allyl carbonates) of triols such as glycerol, trimethylolpropane and tris (hydroxyethyl) isocyanu- 0 rate; 25 tetra(allyl carbonates) of pentaerythritol; hexa(allyl carbonates) of dipentaerythritol; mixed bis(allyl carbonates) of at least two diols F-1- m-a~selected from those listed above; and mixed poly(allyl carbonates) of at least one diol and at least one polyol selected from those listed above.

The following are preferred examples of poly (allyl carbonates) suitable for the purposes of the present invention: bis(allyl carbonate) of diethylene glycol monomer or mixture of monomer and relative oligomers.

The bis (allyl carbonate) of diethylene glycol monomer can be defined with the formula:

CH

2

=CH-CH

2

-CH

2

-CH=CH

2

(I)

0 0 wherein R is the radical of diethylene glycol and n=l.

This compound can be prepared by the reaction of diethylenglycol bis(chloroformate) with allylic alcohol, as described for example in "Encyclopedia of Chemical Technology", Kirk-Othmer, III Ed., Vol. 2, pages 111-112.

20 Bis(allyl carbonate) of diethylene glycol, a a a mixture of monomer (n 1 in formula with one or more oligomers (n from 2 to about 10 in formula can be prepared both simply and conveniently by a transesterification reaction between diallyl carbonate 25 and diethylene glycol, operating in the presence of a basic catalyst, as described for example in European patent 35.304. These mixtures monomer/oligomers can I -I ~r generally contain up to about 80% by weight of oligomers.

(ii) bis(allyl carbonate) of neopentyl glycol monomer or mixture of monomer and relative oligomers.

This bis(allyl carbonate) is similar to that of point above, the diethylene glycol being substituted by neopentyl glycol.

(iii) mixed poly(allyl carbonate) of diethylene glycol and tris(hydroxyethyl) isocyanurate.

This poly(allyl carbonate) can be obtained by the transesterification of diallyl carbonate of a mixture of diethylene glycol and tris(hydroxyethyl) isocyanurate, as described for example in U.S. patent 4.812.545.

(iv) mixed poly(allyl carbonate) of neopentyl glycol and tris(hydroxyethyl) isocyanurate.

This poly (allyl carbonate) is similar to that of point (iii) above, the diethylene glycol being substituted by neopentyl glycol.

mixed poly(allyl carbonate) of 1,4-butandiol and tris(hydroxyethyl) isocyanurate.

This poly (allyl carbonate) is similar to that of point (iii) above, the diethylene glycol being substituted by 1,4-butandiol.

(vi) mixed poly(allyl carbonate) of diethylene 25 glycol and pentaerythritol, described for example in European patent application No. 302.537.

(vii) tris(allyl carbonate) of trimethylol propane, which can be obtained by the reaction of diallyl carbonate with trimethylol propane under transesterification conditions.

(viii) tetrakis(allyl carbonate) of pentaerythritol, which can be obtained by the reaction of diallyl carbonate with pentaerythritol under transesterification conditions.

Suitable transesterification conditions are described for example in European patent 35.304, cited above.

Component B.

prefe^ac4 TheA perketals used as polymerization initiators according to the present invention, are known compounds belonging to the group of gem-diperoxides: R' OOR''' C (II) R" OOR eg wherein: R' represents a tertiary alkyl group and preferably ter-butyl or ter-amyl; R' and R" each independently represent an alkyl group, such as methyl, ethyl, propyl and butyl, said alkyl group possibly having non-interfering functional groups, such as for example an alkyl ester group at the extreme end of the 25 chain; or R' and together with the carbon atom to which they are linked, form a cyclo-alkylenic group and preferably a cyclohexylidenic group, possibly having 13.

one or more alkyl substituents and preferably from 1 to 3 methyl groups.

Examples of these gem-diperoxides are: 2,2-di(terbutyl peroxy) butane; n-butyl 4,4-di(ter-butyl peroxy) valerate; ethyl-3,3-di(ter-butyl peroxy)valerate; 1,1di(ter-butyl peroxy) cyclohexane; and l,l-di(ter-butyl peroxy) 3,3,5-trimethyl-cyclohexane.

Also suitable for t purpose are cyclic gemdiperoxides and cyclic gem-triperoxides, such as for example 3,3,6,6-tetramethyl-l,2,4,5-tetroxane; 3,6diethyl-3,6-dimethyl-l,2,4,5-tetroxane; 7,8,15,16tetraoxadispiro[5.2.5.2]hexadecane; and 3,3,6,6,9,9hexamethyl 1,2,4,5-tetraoxycyclononane.

The perketal is'present in the compositions of the present invention in a quantity of 0.5 to 5.0 parts, and preferably from 0.8 to 2.5 parts by weight, every *oo.

100 parts by weight of component Component Photochromic compounds which are suitable for the purposes of the present invention are selected from the groups of spiropyranes, spiro-oxazines, chromenes and fulgides. Apart from the literature previously cited, examples of spiropiranes are specified in the description of U.S. patent 3.100.778 and British patent 25 1.418.089; examples of spiro-oxazines are indicated in the description of U.S. patents 3.578.602, 4.215.010 and 4.342.668 and in European patent applications No.

14, 134.633, 141.407, 146.135, 432.839 and 432.841; and examples of chromenes are indicated in the description of U.S. patent 3.567.605.

Among the above photochromic compounds those belonging to the class of spiro-oxazines and chromenes are preferred.

Preferred spiro-oxazines are those which can be defined with the formula:

R

i R3 R 4 K N N R2 O R (III) IR (ill)

R

5

X

R

6 wherein: R, R 2 each independently represent a hydrogen atom; a halogen atom (fluorine, chlorine or bromine); or a C 1

-C

5 alkyl group linear or branched; C 1

-C

5 alkoxy group; nitro or cyano group;

.R

3 and R4 each independently represent a C,-C alkyl group linear or branched; phenyl; or benzyl; or

R

3 and R 4 together with the carbon atom to which they are linked form a C 5

-C

8 cyclo-alkyl group; 25 R 5 represents a C 1

-C

5 alkyl group linear or branched, or a similar alkyl group substituted with one or more hydroxy substituent groups, Cl-C, alkoxy or Ci-C carboxyalkyl groups; phenyl; benzyl; or allyl;

R

6 represents a hydrogen atom; a C 1

-C

5 alkyl group linear or branched; or the -NRgR, group, wherein R 8 represents a C 1

-C

5 alkyl group linear or branched, phenyl, or benzyl, and R 9 represents the hydrogen atom, or has the same meaning as Rg, or Rg and R 9 considered together with the nitrogen atom to which they are linked, form a cyclic structure with from 5 to 12 members, possibly containing a further hetero-atom in the chain selected from oxygen and nitrogen;

R

7 represents a hydrogen atom; a halogen atom (fluorine, chlorine or bromine), or a C 1

-C

5 alkyl group linear or branched; a C 1

-C

5 alkoxy group; a cyano group; a nitro group; a sulphide group; a carboxylate ester group with from 1 to 3 carbon atoms in the ester portion; a C 1 -C oxo-alkyl group or a oxo-aryl group; or R represents an aromatic ring or a condensed heterocy- See. clic ring; and X represents CH or N.

In particular when the R i and R 2 groups are different from the iydrogen atom, they can be linked in any of positions 4, 5, 6 and 7 of the indolinic part of the molecule. In addition when the group R 7 is different e from the hydrogen atom or a condensed aromatic or 25 heterocyclic ring, it can be present in any of the positions 9' and 10' of the naphthalene part of the molecule.

16.

-I -I In the preferred embodiment photochromic compounds (III) are used where the substituents have the following meaning:

R

I and Rz independently represent the hydrogen atom or the methyl group; R3 and R 4 both represent the methyl group or jointly represent the cyclohexyl group; Rg represents the methyl group;

R

6 represents the hydrogen atom or the -NR 8 R, group with groups R 8 and R 9 which, together with the nitrogen atom to which they are linked, form a structure having a piperidyl, morpholyl, pyrrolidyl or hexamethylenamine ring;

R

7 represents the hydrogen atom, a nitro group, or an oxomethyl, oxoethyl or oxyphenyl group; and X represents CH.

:In addition, in the preferred embodiment, when the

R

i and R 2 groups are different from hydrogen, they are linked to portions 5 and 6 of the molecule.

Preferred chromenes are those which can be defined Swith the formula:

O*

wheei R R R11 wherein R 1 0 and R 11 each independently represent a 17.

hydrogen atom, a Ci-C 5 alkyl linear or branched, a phenyl group, or a similar phenyl group substituted with from 1 to 5 halogen atoms (fluorine, chlorine or bromine), a cyclopropyl group, or R 10 and R 11 jointly represent a C 5 or C 6 alicyclic group or an adamantane group.

In the polymerizable liquid composition of the present invention component when present, is used in a quantity of from 0.01 to 0.5 parts by weight and preferably in a quantity of about 0.05 parts by weight for every 100 parts by weight of component Component (D) The organic dyes which can be used for colouring the organic glass, can belong to numerous chemical classes, such as for example acridine, anthraquinone, azine, monoazo, disa-o, metallic azo complexes, perinone, benzoquinone, naphthoquinone, formazane, methine, naphthalamide, nitro, nitroso, phthalocyanine, quinacridone and stilbene. The preferred organic dyes of the 20 present invention belong to the classes of anthraqui-

S

none, perinone, monoazo, disazo and phthalocyanine.

Examples of commercial dyes used for the purpose are BLU ESTOFIL RR, ROSSO ESTOFIL BR and GIALLO ESTOFIL 2R (commercial products of Sandoz); SOLVAPERM RED BB, 25 SOLVAPERM YELLOW G and SOLVAPERM BLUE B (commercial products of Hoechst). According to the suppliers, the dyes are of the monoazo, perinone or anthraquinone type.

In the polymerizable liquid composition of the present invention, component when present, is used in a quantity of 0.005 to 0.1 parts by weigiht and preferably in a quantity of about 0.02 parts by weight every 100 parts by weight of component In a particular form of embodiment of the present invention a mixture of dyes and/or photochromic compounds are used, as components and to modify the shade of the optical items, for example, if necessary or desired, to bring the shade to grey or brown, which are preferred by the consumer in the field of optical items.

The polymerizable liquid composition may additionally contain one or more conventional additives such as light stabilizing sterically hindered amines (Hals), lubricants, UV, IR light absorbers and the like, in a global quantity however which does not exceed 1 part by weight for every 100 parts by weight of component A second aspect of the present invention relates to a procedure for the preparation of an organic glass, also coloured or photochromic, which consists in subjecting the above-defined polymerizable liquid 25 composition to radical polymerization.

More specifically the casting technique is used which consists in pouring the polymerizable composition 19.

into a suitably shaped mould and heating it to a temperature within the range of 50 to 120°C, with polymerization times which generally range from 1 to 100 hours.

The use of perketals, according to the present invention, has various advantages with respect to both the process and to the characteristics of the organic glass obtained. In particular perketals can be stored without specific precautions and can be easily and rapidly dissolved in allyl carbonates The polymerization of allyl carbonates catalyzed by perketals allows the production of perfectly hardened polymerized products with good optical characteristics, and consequently of value in the production of optical items such as ophthalmic and safety plates and lenses.

In addition the advantages deriving from the bulk incorporation of the dye or photochromic compound, according to the present invention, are numerous with respect to the techniques of surface application: firstly they represent a great technological simplification, allow a considerable decrease in process s* S costs and an improvement in the production yields, owing to the elimination of the post-treatment operation of the preformed end-product; 25 in addition they ensure a good constancy and repro- Sduction of the shade and intensity of colour, which cannot be achieved with the techniques involving surface application, as these strongly depend on the characteristics of the preformed end-product, such as its hardness; finally, as it is evident in the experimental section which follows, the photochromic characteristics and duration of the photochromic activity (activation/deactivation process life) are considerably enhanced.

In the experimental examples which follow and which provide a further illustration of the invention, the following allyl carbonates are used: (Al) Reaction product of diallyl carbonate (DAC) and diethylene glycol (DEG) in a molar ratio between them of 12/1. The product thus obtained is a mixture of monomer and oligomers of bis(allyl carbonate) of diethylene glycol having the following composition: 0 O

CH

2

=CH-CH

2

-CH

2

-CH

2

-O-CH-CH

2 n-CHg-CH=CH 2 monomer (n 1) 88.3% by weight dimer (n 2) 10.5% by weight trimer (n 3) 1.1% by weight tetramer (n 4) 0.1% by weight Physical-chemical characteristics: S Viscosity, 25 0 C (cst) 13.3 Density, 20°C (g/ml) 1.1519 25 n 20 1.452 (A2) Reaction product of diallyl carbonate (DAC) and neopentylic glycol (NPG) in a molar ratio of 8/1.

S

S

S S

S*

see, 0.:

S

50 55 21.

The product thus obtained is a mixture of monomer and oligomers of bis(allyl carbonate) of neopentyl glycol having the following composition: 0 CH 3 0

CH

2

=CH-CH

2

[-CH

2

C-CH

2 I -CH 2

-CH=CH

2

CH

3 monomer (n 1) 82% by weight dimer (ni 2) 15% by weight trimer (n 3) 2.4% by weight tetramer (n 4) 0.4% by weight Physical-chemical characteristics: Viscosity, 25*C (cst) 53 Density, 20'C (g/ml) 1.096 n D20 1.4525 (A3) Reaction prov _uct of diallyl carbonate (DAC) *with a mixture of diethylene glycol (DEG) and tris- (hydroxyethyl) isocyanurate (THEIC) in the following proportions: DEG 70% by weir t; THEIC 30% by weight; molar ratio DAC/(DEG+THEIC) 4/1.

The product thus obtained is a complex mixture containing: bis(allyl carbonate) of diethylene glycol, monomer oligomers, according to the formula indicated in (Al); tris(allyl carbonate) of tirs~hydroxyeitnyljiso- Secyanurate (monom-,r and oligomers): 22.

[I

CE 2=CH-CE 2- O-C-0-I:CH 2-CH 0 0 11 1 CH 2

-_CH

2 CE 2 CE CE 2 N N 0 -N 0 0 S *5 9 *5 *5 S S

S

S. S S

S

S *5 S

S

*5 S S S. S S

SS

mixed allyl carbonates of diethylene glycol and tris (hydroxyethyl) isocyanurate.

Physical-chemical characteristics: Viscosity, 25*C (cst) Density, 20-C (g/ml) 1.2110 nD 20= 1.465 (M4) Reaction product of diallyl carbonate (DAC) with a mixture of neopentyl glycol (NPG) and tris- 15 (hydroxyethyl) isocyanurate (THEIC) in the following proportions: NPG 70% by weight; THEIC 30% by weight; molar ratio DAC/(NPG+THEIC) 5/1.

The product thus obtained is a complex mixture containing: 20 bis(allyl carbonate) of neopentyl glycol, monomer and oligomers, according to the formula indicated in (A2); tris(allyl carbonate) of tris(hydroxyethyl) isocyanurate, monomer and oligomers, according to the formula indicated in and mixed allyl carbonates of neopentyl glycol and tris (hydroxyethyl) isocyanurate.

23.

Physical-chemical characteristics: Viscosity, 25"C (cst) Density, 20"C (g/ml) 1.1411

D

20 1.4595 (A5) Reaction product of diallyl carbonate (DAC) with a mixture of neopentyl glycol (NPG) and tris- (hydroxyethyl) isocyanurate (THEIC) in the following proportions: NPG 50% by weight; THEIC 50% by weight; molar ratio DAC/(NPG+THEIC) 5/1.

The product thus obtained is a mixture similar to that indicated for having the following physicalchemical characteristics: Viscosity, 25°C (cst) 261 Density, 20"C 1.1820 15 n 20 1.4680

D

(A6) Reaction product of diallyl carbonate (DAC) with a mixture of 1,4-butandiol (BD) and tris(hydroxyethyl) isocyanurate (THEIC) in the following proportions: BD 70% by weight; THEIC 30% by weight; molar 20 ratio DAC/(BD+THEIC) 4/1.

The product thus obtained is a complex mixture containing: bis(allyl carbonate) of 1,4-butandiol (monomer and oligomers): 0 0

CH

2

=CH-CH

2

-CH

2 -CH 2

-CH

2 -CH-0-C-O- n-CH 2

-CH=CH

2 24.

tris(allyl carbonate) of tris(hydroxyethyl) isocyanurate, monomer and oligomers, according to the formula indicated in and mixed allyl carbonates of 1,4-butandiol and tris- (hydroxyethyl) isocyanurate.

Physical-chemical characteristics: Viscosity, 25*C (cst) 39 Density, 20°C (g/ml) 1.1555 n20 1.4592 (A7) Reaction product of diallyl carbonate (DAC) with a mixture of 1,4-butandiol (BD) and tris(hydroxyethyl) isocyanurate (THEIC) in the following proportions: BD 60% by weight; THEIC 40% by weight; molar S" ratio DAC/(BD+THEIC) 3/1.

15 The product thus obtained is a mixture similar to that indicated for having the following physicalchemical characteristics: Viscosity, 25"C (cst) 128 Density, 20°C (g/ml) 1.1880 20 n 20 1.4658 (A8) Tris(allyl carbonate) of trimethylol propane, obtained by reacting diallyl carbonate and trimethylol propane in a molar ratio of 18/1.

This product, mainly monomeric, can be represented by the formula: 0 CH 2 -CH 3 0 CH 2

=CH-CH

2

-CH

2 -C-CH 2 n-CH 2 CH=CH 2 CH 2 -0-C-O-CH.-CH=CH 2 0 (A9) Tetrakis (allyl carbonate) of pentaerythritol, obtained by reacting diallyl carbonate and pentaerythritol in a molarz ratio of 24/1.

This product, mainly monomeric, can be represented by the following formula: 100 CH 2 -O-C-0-CH 2 -CH=CH 2 0.a CH 2 =CH-CH 2 2 -C-CH 2 I -CH 2

-CH=CH

2 CH -0-C-0-CH -CH=CH 2 Reaction product of diallyl carbonate (DAC) :with a mixture of neopentyl glycol (NPG), tris(hydroxyethyl) isocyanurate (THEIC) and pentaerythritol (PE) in the followirw- proportions: NPG 70% by weight; THEIC by weight; PE 20% by weight; molar ratio DAC/(NPG+THEIC+PE) 3/1.

The product thus obtained is a complex mixture of 25 monomers and oligomers ot allyl carbonates of the utilized polyols, having the following physical-chemical characteristics: Viscosity, 25*C (cst) 92 Density, 20*C (g/ml) =1.1367 n D 20=1.4579 26.

(All) Reaction product of diallyl carbonate (DAC) with a mixture of neopentyl glycol (NPG) and pentaerythritol (PE) in the following proportions: NPG 70% by weight; PE 30% by weight; molar ratio DAC/ (NPG+PE) 5/1.

The product thus obtained is a comp-.ex mixture of mornomers and oligomers of allyl carbonates of the utilized polyols, having the following physical-chemical characteristics: Viscosity, 25*C (cst) 97.8 Density, 20'C (g/ml) 1.1355 n201.4575 *In the experimental examples spiro-oxazines (C) .:are also used, which can be represented by the formula: ~13

COH

3 V R14 C N N I (I a)

UOH

3 0 20 R16 (Cl) 1, 3-dihydro-l, 3, 3-trimethyl-spiro(2H-indole- 2,3'-[3H-naphtho-(2,1-b)-(1,4)oxazine]; corresponding to the formula (IIla) wherein all the substituents from

R

12 to R 16 are hydrogen; (C2) mixture of l,3-dihydro-l, 3,3,4, spiro(2H-indole-2,3'-[3H]-naphtho-(2,1-b)-(1,4)-oxazi- 27.

ne], corresponding to the formula (Ila) wherein R 12

R

1

C

3 the other substituents being hydrogen; and of 1,3-dihydro-1, 3,3,5, 6-pentamethyl-spiro[2H-indole- 2,3'-[3H]-naphtho-(2,l-b)-(l,4)-oxazine], correspondir-1 to the formula (Ila) wherein R 13 R 14 CH 3 all the other substituents b~eing hydrogen; (C3) 1, 3-dihydro-6'-piperidino-l, 3, 3-trimethylspiro[2H-indole-2,3'-[3H]-naphtho-(2,l-b) (l,4)-oxazine], corresponding to the formula (Ila) wherein R 1 N-piperidyl, all the other substituents being hydrogen; (C4) 1, 3-dihydro-8 '-oxophenyl-l,3, 3-trimethylspiro[2H-indole-2,3-[3H]-naphtho-(2,1-b)-(1,4)oxazine]; corresponding to the formula (Ila) wherein R 16 C(0)-phenyl, all the other substituents being hydrogen; 1, 3-dihydro-8 '-nitro-l, 3, 3-triemthyl-spiro- [2H-indole-2,3'-[3H]-naphtho-(2,1-b)-(l,4)-oxazine]; corresponding to the formula (Ila) wherein R 16

-NO,

all the other substituents being hydrogen; 20 (C6) 1, 3-dihydro-8 '-oxoethyl-l,3 ,3-trimethylspiro [2H-indole-2, -naphtho- -oxa- *zine] corresponding to the formula (Il~a) wherein R 16 -C C(0)-CH 2

-CH

3 all the other substituents being hydrogen.

In the experimental examples a chromene is also used.

(C7) 3, 3-diphenyl-3H-naphtho[2, l-b]pyrane, having 28.

i the following formula: O- Ph (IVa) wherein Ph phenyl In experimental examples 1 to 12 photochromic lenses are prepared operating in the following way.

The polymerizable liquid compositions are prepared by mixing and homogenizing allyl carbonate perketal 1, 1-di (ter-butylperoxy) -3,3,5-trimethyl cyclohexane (component B) in the quantity indicated in the examples and photochromic compound again in the quantity indicated in the examples. The compositions thus obtained are transformed by polymerization into lenses having a thickness of 2 mm, using the conventional casting technique. According to this technique the S" liquid composition containing the catalyst is poured into the cavities of a mould composed of two glass 20 elements, with a spacing seal of plasticized polyvinyl e chloride or copolymer of ethylene-vinyl acetate (EVA).

The liquid composition is polymerized in the mould by thermal treatment carried out for 5 hours at 85*C plus hours at 90*C and a further 7 hours at 100*C, in an oven with forced circulation. At the end of this treatment, the moulds are opened, the polymerized products are removed and the following characteristics 29.

-e are determined on the photochromic lenses thus obtained: Rockwell Hardness (scale according to the method ASTM D-785; Photochromic properties, determined by recording the visible UV spectra at 23"C in the activated and deactivated forms, with an HP 8452 A (activation by exposure for 60 seconds to a UVA lamp; irradiance 9 W/m 2 The following characteristics of deactivated and activated forms are registered: a) O.D. (lambdax. UVA) and O.D. (lambdamx. vis.): Optical Density values at the wavelenght of the maximum absorption of the UV and visible portions respectively.

b) Y: tristimulus colorimetry value which indi- 15 cates the Luminous Transmittance value in the 0.: visible region, as defined in Regulation CIE 1931 (this is obtained by the mathematical elaboration of the absorption spectra of the two forms, activated and deactivated).

20 c) Photochromic Activity: expressed as delta O.D.

(lambdaX" vis.), difference of O.D. at lambdamx.

in the visible region between activated and 0 deactivated forms and as delta Y, difference between the Y Luminous Transmittance values.

Resistance to fatigue, determined with an Atlas Weather-O-Meter (WOM) equipped with a Xenon 6,500 W lamp (continuous radiation), operating at a I Ia temperature of 63*C on a black reference panel and at a relative humidity of 50%. The aging resistance is determined by measuring, after various periods of exposure in WOM the residuous values of photochromic activity.

Example 1 A composition containing 97.5% by weight of allyl carbonate A4 and 2.5% by weight of l,l-di(terbutylperoxy)-3,3,5-trimethyl cyclohexane is prepared. A quantity of 0.1% by weight of photochromic compound C3 is added to the composition and polymerization is carried out under the conditions previously indicated. Lenses are obtained with a Rockwell hardness equal to 90 and with the following photochromic characteristics: *So 15 Deactivated state O.D. (lambdaa UVA) 2.551 (362 nm) O.D. (lambdamx.vis.) 0.108 (572 nm) Y, 23°C 77.8 Activated state 20 O.D. (lambda vis.) 0.682 (572 nm) Y, 23 0 C 33.6 delta O.D. (lambdaax.vis.) 0.574 (572 nm) delta Y 44.2 The fatigue resistance by exposure in WOM for up to 150 hours produces the following results: 31.

L g I Il 3L~~ Exposure time 50 hrs 100hrs 150hrs -1 0hr delta O.D. (lambdaax.vis.) residual (572 nm) 0.241 0.155 0.087 delta Y, 23°C, residual 29.3 17.6 11.1 Example 2 A composition containing 97.5% by weight of allyl carbonate A4 and 2.5% by weight of l,l-di(terbutylperoxy)-3,3,5-trimethyl cyclohexane is prepared.

A quantity of 0.1% by weight of photochromic compound Cl is added to the composition and polymerization is carried out under the conditions previously indicated.

Lenses are obtained with a Rockwell hardness equal to 86 and with the following photochromic characteristics: 15 Deactivated state O.D. (lambdaax UVA) 2.808 (344 nm) O.D. (lambdax.vis.) 0.050 (598 nm) Y, 23°C 76.0 Activated state 20 O.D. (lambdamx.vis.) 0.316 (598 nm) Y, 23°C 50.9 see& delta O.D. (lambdax.vis.) 0.266 (598 nm) delta Y 25.1 The fatigue resistance by exposure in WOM for up to 150 hours produces the following results: 32.

ill _ul Exposure time 50hrs 100hrs 150hrs delta O.D. (lambda x.vis.) residual (600 nm) 0.267 0.244 0.250 delta Y, 23"C, residual 25.4 26.2 24.5 Example 3 A composition containing 97.5% by weight of allyl carbonate A4 and 2.5% by weight of l,l-di(terbutylperoxy)-3,3,5-trimethyl cyclohexane is prepared. A quantity of 0.1% by weight of photochromic compound C2 is added to the composition and polymerization is carried out under the conditions previously indicated. Lenses are obtained with a Rockwell hardness equal to 91 and with the following photochromic characteristics: Deactivated state 15 O.D. (lambda,, UVA) 3.203 (348 nm) O.D. (lambda×.vis.) 0.063 (610 nm) Y, 23 0 C 73.8 Activated state O.D. (lambdaax.vis.) 0.386 (610 nm) 20 Y, 23°C 44.7 delta O.D. (lambdamx.vis.) 0.323 (610 nm) delta Y 25.1 The fatigue resistance by exposure in WOM for up to 150 hours produces the following results: 33.

I

Exposure time 50hrs 100hrs 150hrs delta O.D. (lambda x.vis.) residual (610 nm) 0.263 0.235 0.225 delta Y, 23*C, residual 21.0 20.6 Example 4 A composition containing 97.5% by weight of allyl carbonate A4 and 2.5% by weight of 1,l-di(terbutylperoxy)-3,3,5-trimethyl cyclohexane is prepared. A quantity of 0.1% by weight of photochromic compound C3 and 0.2% by weight of the commercial HALS stabilizer UVASIL 299 are added to the composition and polymerization is carried out under the conditions previously indicated.

e Lenses are obtained with a Rockwell hardness equal to 90.5 and with the following photochromic charac- 15 teristics: Deactivated state O.D. (lambdaax UVA) 2.793 (360 nm) O.D. (lambdax.vis.) 0.125 (574 nm) Y, 23"C 75.4 20 Activated state O.D. (lambdax.vis.) 0.995 (574 nm) SY, 23°C 23.6 0e delta O.D. (lambdavx.vis.) 0.870 (574 nm) delta Y 51.8 The fatigue resistance by exposure in WOM for up to 150 hours produces the following results: I r Id I Exposure time 50hrs 100hrs 150hrs delta O.D. (lambdamxvis.) residual (572 nm) 0.402 0.250 0.223 delta Y, 23*C, residual 33.0 23.3 19.0 Example A composition containing 97.5% by weight of allyl carbonate A4 and 2.5% by weight of 1,l-di(terbutylperoxy)-3,3,5-trimethyl cyclohexane is prepared. A quantity of 0.1% by weight of photochromic compound C3 and 0.2% by weight of the HALS stabilizer 2,2,6,6-tetramethyl piperidin-4-ol are added to the composition and polymerization is carried out under the conditions previously indicated. Lenses are obtained with a Rockwell hardness equal to 90 and with the following 15 photochromic characteristics: Deactivated state O.D. (lambdamx UVA) 2.774 (362 nm) O.D. (lambda x.vis.) 0.114 (572 nm) Y, 23"C 77.1 *555 20 Activated state O.D. (lambda x.vis.) 0.853 (572 nm) Y, 23°C 28.1 delta O.D. (lambdamxvis.) 0.739 (572 nm) delta Y 49.0 The fatigue resistance by exposure in WOM for up to 150 hours produces the following results: Exposure time 50hrs 100hrs 150hrs delta O.D. (lambda x.vis.) residual (570 nm) 0.738 0.365 0.282 delta Y, 23 0 C, residual 31.2 26.4 19.9 Example 6 A composition containing .99% by weight of allyl carbonate A4 and 1.0% by weight of 1,l-di(terbutylperoxy)-3,3,5-trimethyl cyclohexane is prepared. A quantity of 0.1% by weight of photochromic compound .C3 is added to the composition and polymerization is carried out under the conditions previously indicated. Lenses are obtained with a Rockwell hardness equal to 86 and with the following photochromic characteristics: S. Deactivated state 15 O.D. (lambdaMx UVA) 3.159 (362 nm) O.D. (lambdamx.vis.) 0.116 (572 nm) Y, 23 0 C 77.0 Activated state .e C O.D. (lambdax.vis.) 0.996 (572 nm) *s e 20 Y, 23°C 24.2 delta O.D. (lambdax.vis.) 0.880 (572 nm) delta Y 52.8 The fatigue resistance by exposure in WOM for up to 150 hours produces the following results: 36.

-I

Exposure time 60hrs lOOhrs 150hrs delta O.D. (lambda ,vis.) residual (572 nm) 0.488 0.424 0.416 delta Y, 23"C, residual 37.6 35.8 35.0 Example 7 A composition containing 99% by weight of allyl carbonate A7 and 1.0% by weight of l,l-di(terbutylperoxy)-3,3,5-trimethyl cyclohexane is prepared. A quantity of 0.1% by weight of photochromic compound C3 is added to the composition and polymerization is carried out under the conditions previously indicated. Lenses are obtained with a Rockwell hardness equal to 76 and with the following photochromic characteristics: e* Deactivated state O.D. (lambdamx UVA) 3.142 (364 nm) O.D. (lambdaax.vis.) 0.121 (572 nm) SY, 23 0 C 76.1 Activated state O.D. (lambdax.vis.) 1.010 (572 nm) Y, 23-C 23.5 e* delta O.D. (lambdaux.vis.) 0.889 (572 nm) delta Y 52.6 The fatigue resistance by exposure in WOM for up to 150 hours produces the following results: 37.

Exposure time 60hrs 100hrs 150hrs delta O.D. (lambdamx.vis.) residual (572 nm) 0.447 0.328 0.286 delta Y, 23"C, residual 34.1 28.5 25.7 Example 8 A composition containing 99% by weight of allyl carbonate A3 and 1.0% by weight of 1,1-di(terbutylperoxy)-3,3,5-trimethyl cyclohexane is prepared. A quantity of 0.1% by weight of photochromic compound C3 is added to the composition and polymerization is carried out under the conditions previously indicated.

Lenses are obtained with a Rockwell hardness equal to 80.5 and with the following photochromic characteristics: Deactivated state O.D. (lambdamx UVA) 2.672 (378 nm) O.D. (lambdanx.vis.) 0.111 (574 nm) Y, 23°C 77.9 Activated state O.D. (lambdax.vis.) 0.630 (574 nm) Y, 23"C 36.7 delta O.D. (lambda.x.vis.) 0.519 (574 nm) delta Y 41.2 Example 9 A composition containing 97.5% by weight of allyl carbonate A5 and 2.5% by weight of 1,l-di(terbutylperoxy)-3,3,5-trimethyl cyclohexane is prepared. A quantity of 0.1% by weight of photochromic compound C7 is added to the composition and polymerization is carried out under the conditions -reviously indicated. Lenses are obtained with a Rockwell hardness equal to 95 and with the following photochromic characteristics: Deactivated state O.D. (lambdaa UVA) 1.341 (360 nm) O.D. (lambdaax.vis.) 0.341 (412 nm) Y, 23-C 90.1 Activated state 0.D. (lambda .vis.) 1.026 (412 nm) Y, 23"C 82.8 i.: delta O.D. (lambdaax.vis.) 0.685 (412 nm) Sdelta Y 7.3 The fatigue resistance by exposure in WOM for up to 150 hours produces the following results: Exposure time 50 hours 115 hours S 20 delta O.D. (lambdaax.vis.) 0.567 (412 nm) 0.495 (430 nm) residual delta Y, 23°C, residual 7.0 5.7 Example A composition containing 97.5% by weight of allyl carbonate A5 and 2.5% by weight of l,l-di(terbutylperoxy)-3,3,5-trimethyl cyclohexane is prepared. A quantity of 0.06% by weight of photochromic compound C4 is added 39.

II I sru to the composition and polymerization is carried out under the conditions previously indicated. Lenses are obtained with a Rockwell hardness equal to 94 and with the following photochromic characteristics: Deactivated state O.D. (lambdamx UVA) 2.969 (340 nm) O.D (lamb, ris.) 0.062 (614 nm) Y, 23°C 62.5 Activated state O.D. (lambda.ovis.) 0.868 (614 nm) Y, 23°C 25.2 .i delta O.D. (lambda×x.vis.) 0.806 (614 nm) Sdelta Y 37.3 Example 11 SA composition containing 97.5% by weight of allyl carbonate A5 and 2.5% by weight of l,l-di(terbutylperoxy)-3,3,5-trimethyl cyclohexane is prepared. A quantity •of 0.06% by weight of photochromic compound C5 is added 20 to the composition and polymerization is carried out unuer the conditions previously indicated. Lenses are obtained with a Rockwell hardness equal to 94 and with the following photochromic characteristics: Deactivated state O.D. (2ambda x UVA) 1.661 (330 nm) O.D. (lambdamavis.) 0.066 (612 nm) Y, 23°C 72.6 ~111 -1 Activated state O.D. (lambda x.vis.) 0.195 (612 nm) Y, 23°C 60.6 delta O.D. (lambdam.vis.) 0.129 (612 nm) delta Y 12.0 Example 12 A composition containing 97.5% by weight of allyl carbonate A5 and 2.5% by weight of l,l-di(-terbutylperoxy)-3,3,5-trimethyl cyclohexane is prepared. A quantity of 0.06% by weight of photochromic compound C6 i.3 added to the composition and polymerization is carried out S* under the conditions previously indicated. Lenses are obtained with a Rockwell hardness equal to 92 and with the following photochromic characteristics: Deactivated state O.D. (lambdax UVA) 2.904 (334 nm) O.D. (lambdaax.vis.) 0.070 (614 nm) Y, 23"C 63.2 20 Activated state O.D. (lambdam.vis.) 0.762 (614 nm) Y, 23"C 28 delta 0,D. (lambdam.vis.) 0.692 (614 nm) delta Y 35.2 In experimental examples 13 to 27 coloured lenses are prepared operating in the following way.

The polymerizable liquid compositions are prepared by mixing and homogenizing allyl carbonate perketal l,l-di(ter-butylperoxy)-3,3,5-trimethyl cyclohexane (component B) in the quantity indicated in the examples and dye again in the quantity specified in the examples. The compositions are transformed by polymerization into lenses with a thickness of 2 mm or 3 mm using the conventional casting technique. The liquid composition is polymerized by thermal treatment, carried out in an oven with forced circulation, according to the following program: 85°C for 5 hours, for 15 hours and 100*C for hours. At the end of this treatment the moulds are opened, the polymerized *o products are recovered and the following characteristics are determined on the lenses thus obtained: Transmittance in the visible range measured using a Gardner Hazegard XL-211 apparatus (ASTM D-1003); Rockwell Hardness measured with a Rockwell durometer (ASTM D-785); colour, expressed with colorimetric values a* and according to Regulation CIE 1976. The measurement is carried out using a MACBETH 1500 PLUS spectrophotometer under the following measurement conditions: illuminant source type C/2"; specularity excluded; UV excluded.

Examples 13-20 42.

I A composition containing 97.5% by weight of allyl carbonate A5 and 2.5% by weight of l,l-di(terbutylperoxy)-3,3,5-trimethyl cyclohexane is prepared. The following dyes mentioned by their commercial names are added to the composition, in the quantities indicated, expressed in percentage by weight of the composition itself: example 13: BLU ESTOFIL RR, 0.025%; example 14: SOLVAPERM BLUE B, 0.025%; example 15: SOLVAPERM RED BB, 0.025%; *fle..

example 16: GIALLO ESTOFIL 2R, 0.050%; .e *e example 17: ROSSO ESTOFIL BR, 0.050%; example 18: BLU ESTOFIL RR, 0.015%; example 19: GIALLO ESTOFIL 2R; 0.050%; example 20: SOLVAPERM RED BB, 0.020%.

Polymerization is carried out under the conditions described above and lenses are produced having a thickness of 3 mm (examples 13-17) or 2 mm (examples 18-20) and the characteristics indicated in the follo- 20 wing table are determined on the lenses.

Es.No Hardness Transmit.(%) L* a* b* 13 111 8.7 34.6 30.1 -61.1 14 110 4.6 24.4 7.9 -24.9 15 111 20.3 51.8 75.9 30.7 16 111 89.1 95.3 -24.9 76.4 17 111 22.8 53.5 64.8 98.3 43.

I I_, 18 103 33.6 64.2 5.4 -39.8 19 108 89.7 95.2 -24.6 72.3 109 24.1 60.1 73.8 2.3 Examples 21-23 A composition containing 97.5% by weight of allyl carbonate Al and 2.5% by weight of 1,l-di(terbutylperoxy)-3,3,5-trimethyl cyclohexane is prepared. The following dyes mentioned by their commercial names are added to the composition, in the quantities indicated, expressed in percentage by weight of the composition Sitself: example 21: BLU ESTOFIL RR, 0.015%; example 22: GIALLO ESTOFIL 2R, 0.050%; example 23: SOLVAPERM RED BB, 0.020%.

Polymerization is carried out under the conditions described above and lenses having a thickness of 2 mm I are produced and the characteristics shown in the table below are determined on the lenses.

Es.No Hardness Transmit.(%) L* a* b 0 20 21 86 46.3 71.8 -2.2 -18.0 22 85 90.3 94.5 -23.9 67.8 23 85 46.4 70.6 46.8 Examples 24-27 A composition containing 98.5% by weight of allyl carbonate A3 and 1.5% by weight of 1,l-di(terbutylperoxy)-3,3,5-trimethyl cyclohexane is prepared. The 44.

1 I following dyes mentioned by their commercial names are added to the composition, in the quantities indicated, expressed in percentage by weight of the composition itself: example 24: BLU ESTOFIL RR, 0.015%; example 25: GIALLO ESTOFIL 2R, 0.050%; example 26: SOLVAPERM RED BB, 0.020%.

example 27: SOLVAPERM YELLOW G, 0.050%.

Polymerization is carried out under the conditions described above and lenses having a thickness of 2 mm St are produced and the characteristics shown in the table below are determined on the lenses.

Es.No Hardness Transmit.(%) L* a b 24 90 29.9 62.3 1.5 -34.9 25 94 89.9 95.3 -24.6 70.7 ***to 26 90 32.5 63.0 69.6 -4.1 27 84 84.3 93.1 -18.5 99.6 The results of examples 13-27 are shown in the 20 graphics of figures 1,2,3 and 4 enclosed, wherein the pairs of values a* and b* allow a rapid visualization of the shades of each product.

In examples 28 to 34 below, colourless flat plates are prepared.

In particular the preparation of the plates is carried out by adding 1,1-di(terbutylperoxy)-3,3,5trimethylcyclo hexane, as initiator, to the allyl carbonate, in a quantity of 2.5% by weight in the mixture. The compositions containing the catalyst are transformed by polymerization into flat plates with a thickness of 3 mm by the conventional casting technique. According to this technique the liquid composition containing the catalyst is poured into the cavity of a mould composed of two glass elements, with a spacing seal of plasticized polyvinyl chloride or copolymer of ethylene-vinyl acetate (EVA)..The liquid composition is polymerized by thermal treatment carried e out in an oven with forced circulation, according to the following program: 85°C for 7 hours, 90"C for 16 hours and 100*C for 7 hours. At the end of this treatment, the moulds are opened, the polymerized products are removed and are maintained at 110°C for a f' her 2 hours, to decompose any possible residuous inii .or and relax any possible internal tension.

The following characteristics are determined on .the plates thus obtained: 20 a) Optical characteristics: Refractive Index (n 20 measured with an Abbe refractometer (ASTM D-542); Haze and Transmittance in visible range measured using a Hazegard XL-211 device of Gardner (ASTM D-1003); Yellowness index (YI) (ASTM D-1925) defined as: 100 YI (1.277X 1.06Z)

Y

determined with a MACBETH 1500 Plus spectrophotometer.

b) Physical and mechanical characteristics: Density: determined with a hydrostatic balance at a temperature of 20"C (ASTM D-792); Volume contraction during polymerization (Shrinkage), calculated with the following formula: **oo: (polymer density monomer density) Shrinkage x 100 (polymer density) Rockwell Hardness measured with a Rockwell durometer (ASTM D-785); Izod Impact Strength (ASTM D-256 unnotched).

Heat distortion temperature under load ec. 1.82 MPa (HDT) (ASTM D-648).

Example 28 20 A polymerizable liquid composition containing 97.5% by weight of allyl carbonate Al and 2,5% by weight of 1,l-di(terbutylperoxy)-3,3,5-trimethyl cyclohexane is prepared and polymerization is carried out by casting under the conditions described above.

The plates obtained are perfectly polymerized, transparent and without optical defects and have the following characteristics: 47.

I

no u 1.4894 Haze 0.17 Transmittance 92.6 YI 1.80 Density, 20*C 1.2105 Shrinkage Rockwell Hardness, M 100 Izod (KJ/m 2 6.7 HDT 72.5 Example 29 A polymerizable liquid composition containing 97.5% by weight of allyl carbonate A2 and 2.5% by weight of 1,l-di(terbutylperoxy)-3,3,5-trimethyl cyclohexane is prepared and polymerization is carried 15 out by casting under the conditions described above.

e. The plates thus obtained have the following characteristics: n 20 1.4948 Haze 0.18 20 Transmittance 92.5 e"o YI 2.3 Density, 20'C 1.2485 Shrinkage 8.6 Rockwell Hardness, M 105 Izod (KJ/m 2 17.3 HDT 76 48.

I II IL g~s

I

Example A polymerizable liquid composition containing 97.5% by weight of allyl carbonate A3 and 2.5% by weight of 1,1-di(terbutylperoxy)-3,3,5-trimethyl cyclohexane is prepared and polymerization is carried out by casting under the conditions described above.

The plates thus obtained have the following characteristics: n 20 1.5010 Haze 0.22 Transmittance 91.4 YI 4.6 Density, 20 0 C 1.2910 Shrinkage 15 Rockwell Hardness, M 116 SIzod (KJ/m 2 10.7 HDT 100 Example 31 A polymerizable liquid composition containing 97.5% by weight of a mixture of allyl carbonates A2 and ses A8 (ratio by weight 70/30) and 2.5% by weight of 1,1di(terbutylperoxy)-3,3,5-trimethyl cyclohexane is prepared and polymerization is carried out by casting under the conditions described above. The plates thus obtained have the following characteristics: n 0 20 1.4925 Haze 0.3 49.

0 o* 99* .9* 9 9 9 99* 9 o *o o oo o* Transmittance 92.2 YI Density, 20°C 1.2282 Rockwell Hardness, M 104 Izod (KJ/m 2 6.3 HDT 130 Example 32 A polymerizable liquid composition containing 97.5% by weight of a mixture of allyl carbonates A2 and A9 (ratio by weight 70/30) and 2.5% by weight of 1,1di(terbutylperoxy)-3,3,5-trimethyl cyclohexane is prepared and polymerization is carried out by casting under the conditions described above. The plates thus obtained have the following characteristics: 15 n 20 1.4929 Haze 0.4 Transmittance 92.0 YI 2.9 Density, 20°C 1.2426 Rockwell Hardness, M 117 Izod (KJ/m 2 6.1 HDT 130 Example 33 A polymerizable liquid composition containing 97.5% by weight of allyl carbonate A6 and 2.5% by weight of 1,1-di(terbutylperoxy)-3,3,5-trimethyl cyclohexane is prepared and polymerization is carried 99 oo 99 9 9 .9 99 I out by casting under the conditions described above.

The plates thus obtained have the following characteristics: noD 20 1.5012 Haze 0.26 Transmittance 92.5 YI 1.87 Density, 20"C 1.2882 Shrinkage 10.3 Rockwell Hardness, M 96 Izod (KJ/m 2 19.5 HDT Example 34 **Got: 0 A polymerizable liquid composition containing .i 15 97.5% by weight of allyl carbonate A7 and 2.5% by weight of l,l-di(terbutylperoxy)-3,3,5-trimethyl cyclohexane is prepared and polymerization is carried out by casting under the conditions described above.

*S *S The plates thus obtained have the following characteristics: n 20 1.5030

OVOO:

Haze 0.22 Transmittance 92.0 YI 3.89 Density, 20°C 1.3064 Shrinkage 9.1 Rockwell Hardness, M 98 51.

Izod (KJ/m 2 30.5 HDT 66 In examples 35 and 36 which follow, colourless flat plates are prepared.

In particular the preparation of the plates is carried out by adding 1,l-di(terbutylperoxy)-3,3,5trimethylcyclo hexane, as initiator, to the allyl carbonate, in a quantity of 2.0% by weight in the mixture. The compositions containing the catalyst are transformed by polymerization into flat plates with a thickness of 3 mm by the conventional casting technique. According to this technique the liquid composition containing the catalyst is poured into the cavity of a mould composed of two glass elements, with 15 a spacing seal of plasticized polyvinyl chloride or copolymer of ethylene-vinyl acetate (EVA). The liquid composition is polymerized by thermal treatment carried out in an oven with forced circulation for 24 hours at 4 95°C. At the end of this treatment, the moulds are cpened, the polymerized products are removed and are maintained at 110 0 C for a further 2 hours, to decompose *4*440 any possible residuous initiator and relax any possible internal tension. On the plates thus obtained, the above described characteristics are evaluated.

Example A polymerizable liquid composition containing 98% by weight of allyl carbonate A10 and 2% by weight of 52.

I

l,l-di(terbutylperoxy)-3,3,5-trimethyl cyclohexane is prepared and polymerization is carried out by casting under the conditions described above. The plates thus obtair'' have the following characteristics: nt 2 1.4935 Haze 0.25 Transmittance 92.7 YI 1.60 Density, 20*C 1.2483 Shrinkage Rockwell Hardness, M 105 Izod (KJ/m 2 22 HDT 101 Example 36 A polymerizable liquid composition containing 98% by weight of allyl carbonate A7 and 2% by weight of 1,1-di(terbutylperoxy)-3,3,5-trimethyl cyclohexane is prepared and polymerization is carried out by casting under the conditions described above. The plates thus obtained have the following characteristics: nD 20 1.4930 o o Haze Transmittance

YI

Density, 20°C Shrinkage Rockwell Hardness, M 0.30 92.8 1.25 1.2501 9.2 108 Izod (KJ/m 2 16 HDT 170 54.

Claims (6)

1. Liquid composition which can be polymerized, via radicals, into organic glasses also coloured and/or photochromic, including a polymerizable allyl car- bonate, a polymerization initiator capable of gener- ating free radicals under polymerization conditions and possibly also a dye and/or photochromic compound, characterized in that: said polymerizable allyl carbonate is at least a poly(allyl carbonate) of an aliphatic C 3 -J 10 poly- ol, linear or branched, or of a cyclo-aliphatic C 5 -C 16 polyol, said polyols containing from 2 to 6 hydroxyl groups in the molecule, said poly(allyl i carbonates) being in the form of monomers or 15 mixtures of monomer and relative oligomers; said polymerization initiator, generator of free radicals, is at least a compound selected from the group of perketals; said photochromic compound is at least an organic photochromic compound selected from the groups of spiropyranes, spiro-oxazines, chromenes and fulgides; and said dye is at least an organic dye.

2. Composition according to claim 1, characterized in that said poly(allyl carbonates) are selected from: bis(allyl carbonates) of diols: diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, 1,3-propandiol, 1,4-butandiol, 1,6-hexandiol, neopentyl glycol, 3-methyl-1,5-pentan- diol, 2-methyl-2-ethyl-l,3-propandiol, 2,2-diethyl-l,3- propandiol, 2,2,4-trimethyl-l,3-pentandiol, 1,4-dime- thylolcyclohexane and 4,8-bis(hydroxymethyl)- [5.2.1.0 2 6 tricyclodecane; tris(allyl carbonates) of triols: glycerol, tri- methylolpropane and tris (hydroxyethyl) isocyanu- rate; tetra(allyl carbonate) of pentaerythritol; hexa(allyl carbonate) of dipentaerythritol; mixed bis(allyl carbonates) of at least two diols selected from those listed above; and mixed poly(allyl carbonates) of at least one diol 15 and at least one polyol selected from those listed above.

3. Composition according to claim 2, characterized in that said poly(allyl carbonates) are: bis(allyl carbonate) of diethylene glycol monomer or mixture of monomer and relative oligomers; o (ii) bis(allyl carbonate) of neopentyl glycol monomer or mixture of monomer and relative oligomers; (iii) mixed poly(allyl carbonate) of diethylene S" glycol and tris(hydroxyethyl) isocyanurate; (iv) mixed poly(allyl carbonate) of neopentyl glycol and tris(hydroxyethyl) isocyanurate; mixed poly(allyl carbonate) of 1,4-butandiol

56. and tris(hydroxyethyl) isocyanurate; (vi) mixed poly(allyl carbonate) of diethylene glycol and pentaerythritol; (vii) tris(allyl carbonate) of trimethylol pro- pane; or (viii) tetrakis(allyl carbonate) of pentaeryth- ritol. 4. Composition according to claim 1, characterized in that component is selected from gem-diperoxides: R' OOR' C R' (II) R" OOR' wherein: R represents a tertiary alkyl group 15 and preferably ter-butyl or ter-amyl; R' and R" each independently represent an alkyl group, such as methyl, ethyl, propyl and butyl, said alkyl group possibly having non-interfering functional groups, such as for example an alkyl ester group at the extreme end of the 20 chain; or R' and together with the carbon atom to which they are linked, form a cyclo-alkylenic group and preferably a cyclohexylidenic group, possibly having one or more alkyl substituents and preferably from 1 to 3 methyl groups; cyclic gem-diperoxides; and cyclic 25 gem-triperoxides. Composition according to claim 4, characterized in that said component is selected from 2,2-di(ter- butyl peroxy) butane; n-butyl 4,4-di(ter-butyl peroxy) valerate; ethyl-3,3-di(ter-butyl peroxy)valerate; 1,1-

57. di (ter-butyl peroxy) cyclohexane; 1,1-di (ter-butyl peroxy) 3,3,5-trimethyl-cyclohexane, 3,3,6,6-tetramethyl-1,2,4,5-tetroxane; 3,6-diethyl-3,6-dimethyl-1,2,4,5-tetroxane; 7,8,15,16-tetraoxadispiro[5.2.5.2]-hexadecane; and 3,3,6,6,9,9-hexamethyl 1,2,4,5- tetraoxycyclononane. 6. Composition according to claim 1, characterized in that it contains said component in a quantity of 0.5 to 5.0 parts, every 100 parts by weight of component 7. Composition according to claim 6 characterized in that it contains said component B in a quantity of from 0.8 to 2.5 parts by weight for every 100 parts by weight of component A. 8. Compositions according to claim 1, characterized in that said component is selected from spiro-oxazines having the formula: ooooo o C *o 25 C o: 25 wherein: R 1 R 2 each independently represent a hydrogen atom; a halogen atom (fluorine, chlorine or bromine); or a C 1 -C 5 alkyl group linear or branched; C 1 -C 5 alkoxy group; nitro or cyano group; R 3 and R 4 each independently represent a C 1 -C 5 alkyl C C group linear or branched; phenyl; or benzyl; or R 3 and R 4 together with the carbon atom to which they are linked form a C 5 -C 8 cyclo-alkyl group; R represents a C 1 -C 5 alkyl group linear or branched, or a similar alkyl group substituted with one or more hydroxy substituent groups, Ci-C 5 alkoxy or Ci-C carboxyalkyl groups; phenyl; benzyl; or allyl; R 6 represents a hydrogen atom; a Cl-C 5 alkyl group linear or branched; or the -NRgR group, wherein R 8 represents a C 1 -C 5 alkyl group linear or branched, phenyl, or benzyl, and R9 represents the hydrogen atom, or has the same meaning as Rs, or R and R9, considered together with the nitrogen atom to which they are linked, form a cyclic structure with from 5 to 12 members, possibly containing a further hetero-atom in the chain selected from oxygen and nitrogen; S. R, represents a hydrogen atom; a halogen atom (fluorine, chlorine or bromine), or a Ci-C 5 alkyl group linear or branched; a C 1 -C 5 alkoxy group; a cyano group; 20 a nitro group; a sulphide group; a carboxylate ester group with from 1 to 3 carbon atoms in the ester portion; a C -C 5 oxo-alkyl group or a oxo-aryl group; or R 7 represents an aromatic ring or a condensed heterocy- clic ring; and 25 X represents CH or N. 9. Composition according to claim 8, characterized in that in said formula (III): It, R 1 and R2 independently represent the hydrogen atom or the methyl group; R3 and R4 both represent the methyl group or jointly represent the cyclohexyl group; Rg represents the methyl group; R 6 represents the hydrogen atom or the group with groups Rg and R 9 which, together with the nitrogen atom to which they are linked, form a structure having a piperidyl, morpholyl, pyrrolidyl or hexamethylenamine ring; R 7 represents the hydrogen atom, a nitro group, or an oxomethyl, oxoethyl or oxyphenyl group; and X represents CH. Composition according to claim 1, characterized in that said component is selected from chromenes having formula: ***ee 200 wherein R10 and R,1 each independently represent a hydrogen atom, a Ci-C 5 alkyl group linear or branched, a phenyl group, or a similar phenyl group substituted "with from to 5 halogen atoms (fluorine, chlorine or wherein R 10 and R 1 each independently represent a hydrogen atom, a C 1 -C alkyl group linear or branched, a phenyl group, or a similar phenyl group substituted with from 1 to 5 halogen atoms (fluorine, chlorine or 25 bromine), a cyclopropyl group, or R, 1 and R 11 jointly represent a CS or C 6 alicyclic group or an adamantane group. 11. Composition according to claim 1, characterized in that it contains said component in a quantity of 0.01 to 0.5 parts by weight for every 100 parts by weight of component 12. A composition according to claim 11 characterized in that it contains component in a quantity of about 0.05 parts by weight for every 100 parts by weight of component 13. Composition according to claim 1, characterized in that said component is selected from those of the following groups: acridine, anthraquinone, azine, monoazo, disazo, metallic azo complexes, perinone, benzoquinone, naphthoquinone, formazane, methine, naphthalamide, nitro, nitroso, phthalocyanine, quinacridone and stilbene. 14. Composition according to claim 13, characterized in that said component is selected from those of anthraquinone, perinone, monoazo, disazo and phthalo-cyanine. Composition according to claim 1, characterized in that it contains said component in a quantity of 0.005 to 0.1 parts by weight for every 100 parts by weight of component 16. Composition according to claim 15 characterized in that it contains said component in a quantity of about 0.02 parts by weight for every 100 parts by weight of component 25 17. Composition according to claim 1, characterized in that it additionally contains one or more additives selected from stabilizers, such as light stabilizing sterically hindered amines (Hals), lubricants, UV, IR light absorbers and the like, in a global quantity however which does not exceed 1 part by weight for

61. every 100 parts by weight of component 18. Procedure for the preparation of an organic glass, also coloured or photochromic, characterized in that the polymerizable liquid composition according to claims 1-17 is subjected to radicalic polymerization. 19. Procedure according to claim 18, characterized in that the polymerization is carried out with the casting technique by pouring the polymerizable composition into moulds and heating it to temperatures within the range of 50 to 120°C, with polymerization times which generally vary from 1 to 100 hours. Organic glasses obtained according to the procedure of claims 18 or 19. 21. A liquid composition according to claim 1 substantially as herein described with reference to any one of the Examples. DATED this 2nd day of February, 1995 0* C C. C C S PHILLIPS ORMONDE FITZPATRICK ATTORNEYS FOR: ENICHEM SYNTHESIS S.p.A. A 4- C CCC I CAWINWOIDM ACKIlMlAYW122200 RLIB CASE 3590 COMPOSITION AND PROCEDURE FOR THE PREPARATION OF ORGANIC GLASSES. Abstract 000o0: A polymerizable liquid composition includes 5 a polymerizable poly(allyl carbonate) of an aliphatic or cyclo-aliphatic polyol; o* an organic peroxide generator of free radicals selected from the group of perketals, and possibly S- an organic dye and/or an organic photochromic e* e compound. The compositions can be transformed, by bulk polymerization, into an organic glass which is colour- less, or coloured or photochromic, having good optical and mechanical characteristics. I I